US5348976A - Condensed heterocyclic derivatives and agricultural or horticultural fungicides containing the same - Google Patents
Condensed heterocyclic derivatives and agricultural or horticultural fungicides containing the same Download PDFInfo
- Publication number
- US5348976A US5348976A US08/117,284 US11728493A US5348976A US 5348976 A US5348976 A US 5348976A US 11728493 A US11728493 A US 11728493A US 5348976 A US5348976 A US 5348976A
- Authority
- US
- United States
- Prior art keywords
- group
- sub
- ethyl
- methyl
- hydrogen atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000417 fungicide Substances 0.000 title claims abstract description 21
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 20
- -1 2-indolyl group Chemical group 0.000 claims abstract description 83
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 230000000855 fungicidal effect Effects 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 31
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 26
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 19
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 241000233866 Fungi Species 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 5
- 150000004292 cyclic ethers Chemical group 0.000 claims description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001041 indolyl group Chemical group 0.000 claims description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 2
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 claims description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 3
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 1
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 claims 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 claims 1
- 230000000243 photosynthetic effect Effects 0.000 claims 1
- 241000233679 Peronosporaceae Species 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- 230000006378 damage Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 88
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 69
- 239000000203 mixture Substances 0.000 description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000004480 active ingredient Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000000543 intermediate Substances 0.000 description 13
- 239000012044 organic layer Substances 0.000 description 13
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 240000008067 Cucumis sativus Species 0.000 description 10
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000004563 wettable powder Substances 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YOETUEMZNOLGDB-UHFFFAOYSA-N 2-methylpropyl carbonochloridate Chemical compound CC(C)COC(Cl)=O YOETUEMZNOLGDB-UHFFFAOYSA-N 0.000 description 7
- 229940024606 amino acid Drugs 0.000 description 7
- 235000001014 amino acid Nutrition 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 6
- 241000233622 Phytophthora infestans Species 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 241001281805 Pseudoperonospora cubensis Species 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 241000219095 Vitis Species 0.000 description 6
- 235000009754 Vitis X bourquina Nutrition 0.000 description 6
- 235000012333 Vitis X labruscana Nutrition 0.000 description 6
- 235000014787 Vitis vinifera Nutrition 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 230000003902 lesion Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- SZXBQTSZISFIAO-ZETCQYMHSA-N (2s)-3-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]butanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC(=O)OC(C)(C)C SZXBQTSZISFIAO-ZETCQYMHSA-N 0.000 description 5
- 241000227653 Lycopersicon Species 0.000 description 5
- 150000003862 amino acid derivatives Chemical class 0.000 description 5
- 201000010099 disease Diseases 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- 239000004495 emulsifiable concentrate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 241001281803 Plasmopara viticola Species 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 208000015181 infectious disease Diseases 0.000 description 4
- 238000011081 inoculation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011369 resultant mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- BOEQBJGCRDSQAI-ZETCQYMHSA-N (2s)-3-methyl-2-(propan-2-yloxycarbonylamino)butanoic acid Chemical compound CC(C)OC(=O)N[C@@H](C(C)C)C(O)=O BOEQBJGCRDSQAI-ZETCQYMHSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 2
- USQFZXPVBWZABE-UHFFFAOYSA-N 2-amino-n-[1-(5-chloro-1-benzofuran-2-yl)ethyl]-3-methylbutanamide;hydrochloride Chemical compound Cl.ClC1=CC=C2OC(C(C)NC(=O)C(N)C(C)C)=CC2=C1 USQFZXPVBWZABE-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 230000000843 anti-fungal effect Effects 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 244000053095 fungal pathogen Species 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- IVRIRQXJSNCSPQ-UHFFFAOYSA-N propan-2-yl carbonochloridate Chemical compound CC(C)OC(Cl)=O IVRIRQXJSNCSPQ-UHFFFAOYSA-N 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 2
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 2
- JRPPYJVOUAZFCB-UHFFFAOYSA-N 1,5-bis(5-chloro-1-benzofuran-2-yl)pentan-3-one Chemical compound ClC1=CC=C2OC(CCC(=O)CCC=3OC4=CC=C(C=C4C=3)Cl)=CC2=C1 JRPPYJVOUAZFCB-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- VBNMNLNTLNOVIT-UHFFFAOYSA-N 1-(1h-indol-3-yl)ethanamine Chemical compound C1=CC=C2C(C(N)C)=CNC2=C1 VBNMNLNTLNOVIT-UHFFFAOYSA-N 0.000 description 1
- SNOAYFXWANUNRY-UHFFFAOYSA-N 1-(2,3-dihydro-1-benzofuran-2-yl)ethanamine Chemical compound C1=CC=C2OC(C(N)C)CC2=C1 SNOAYFXWANUNRY-UHFFFAOYSA-N 0.000 description 1
- UXKMJXGBXBAIJA-UHFFFAOYSA-N 1-(3-methyl-1-benzothiophen-2-yl)ethanamine Chemical compound C1=CC=C2C(C)=C(C(N)C)SC2=C1 UXKMJXGBXBAIJA-UHFFFAOYSA-N 0.000 description 1
- ZONXHDVNHVWYHH-UHFFFAOYSA-N 1-(3-methyl-1h-indol-2-yl)ethanamine Chemical compound C1=CC=C2C(C)=C(C(N)C)NC2=C1 ZONXHDVNHVWYHH-UHFFFAOYSA-N 0.000 description 1
- DVYLBXVDCSGLLN-UHFFFAOYSA-N 1-(5-fluoro-1-benzofuran-2-yl)ethanamine Chemical compound FC1=CC=C2OC(C(N)C)=CC2=C1 DVYLBXVDCSGLLN-UHFFFAOYSA-N 0.000 description 1
- VWZRQXBKTGFEMT-UHFFFAOYSA-N 1-(5-fluoro-1-benzothiophen-2-yl)ethanamine Chemical compound FC1=CC=C2SC(C(N)C)=CC2=C1 VWZRQXBKTGFEMT-UHFFFAOYSA-N 0.000 description 1
- NLYIVIRAFQNXFQ-UHFFFAOYSA-N 1-(6-chloro-1-benzothiophen-2-yl)-N-methoxyethanimine Chemical compound C1=C(Cl)C=C2SC(C(C)=NOC)=CC2=C1 NLYIVIRAFQNXFQ-UHFFFAOYSA-N 0.000 description 1
- KSQGUWGZPFFIAB-UHFFFAOYSA-N 1-(6-chloro-1-benzothiophen-2-yl)ethanamine Chemical compound C1=C(Cl)C=C2SC(C(N)C)=CC2=C1 KSQGUWGZPFFIAB-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006019 1-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000006183 2,4-dimethyl benzyl group Chemical group [H]C1=C(C([H])=C(C(=C1[H])C([H])([H])*)C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FQVVIXFASKDYMW-UHFFFAOYSA-N 2-(1-aminoethyl)-1-benzofuran-5-carbonitrile Chemical compound N#CC1=CC=C2OC(C(N)C)=CC2=C1 FQVVIXFASKDYMW-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZHCPQHVVAUVVMF-UHFFFAOYSA-N 2-amino-3-methyl-n-[1-(5-nitro-1-benzofuran-2-yl)ethyl]butanamide Chemical compound [O-][N+](=O)C1=CC=C2OC(C(C)NC(=O)C(N)C(C)C)=CC2=C1 ZHCPQHVVAUVVMF-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 description 1
- 241000235349 Ascomycota Species 0.000 description 1
- 241000221198 Basidiomycota Species 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010017533 Fungal infection Diseases 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 241000233654 Oomycetes Species 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 description 1
- 241000233614 Phytophthora Species 0.000 description 1
- 241000233626 Plasmopara Species 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 241001281802 Pseudoperonospora Species 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PHHWLDOIMGFHOZ-UHFFFAOYSA-L disodium;dinaphthalen-1-ylmethanedisulfonate Chemical compound [Na+].[Na+].C1=CC=C2C(C(C=3C4=CC=CC=C4C=CC=3)(S(=O)(=O)[O-])S([O-])(=O)=O)=CC=CC2=C1 PHHWLDOIMGFHOZ-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- XNXVOSBNFZWHBV-UHFFFAOYSA-N hydron;o-methylhydroxylamine;chloride Chemical compound Cl.CON XNXVOSBNFZWHBV-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- CPGWSLFYXMRNDV-UHFFFAOYSA-N n-methyl-n-phenylcarbamoyl chloride Chemical compound ClC(=O)N(C)C1=CC=CC=C1 CPGWSLFYXMRNDV-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 125000006503 p-nitrobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1[N+]([O-])=O)C([H])([H])* 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ASBCPDXIOKZART-UHFFFAOYSA-N tert-butyl n-[1-[1-(5-chloro-1-benzofuran-2-yl)ethylamino]-2,3-dimethyl-1-oxobutan-2-yl]carbamate Chemical compound ClC1=CC=C2OC(C(C)NC(=O)C(C)(NC(=O)OC(C)(C)C)C(C)C)=CC2=C1 ASBCPDXIOKZART-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
- A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
- A01N47/14—Di-thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D307/81—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/20—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 hydrogenated in the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D333/58—Radicals substituted by nitrogen atoms
Definitions
- the present invention relates to a condensed heterocyclic derivative as well as an agricultural or horticultural fungicide containing the same as an active ingredient.
- the present invention also relates to a process for preparing the condensed heterocyclic derivative.
- aminoacid amide derivatives have been known as a pesticide and also as a herbicide.
- aminoacid amide derivatives include N-(tert-butoxycarbonyl)-L-valine-4-methoxyphenylethylamide (Japanese Patent Application First Publication No. Hei 3-5,451), N 2 -phenoxycarbonyl-N 1 -[racemi-1-(4-chlorophenyl)ethyl]-L-isoleucinamide (Japanese Patent Application First Publication No.
- Hei 4-283,554 benzyl ⁇ (D,L)-1-[(3,4-dimethoxyphenethyl)carbamoyl]-n-butyl ⁇ carbamate (Japanese Patent Application First Publication No. Hei 4-308,507), N-(i-propyloxycarbonyl)-L-valine-diphenylmethylamide (Japanese Patent Application First Publication No. Hei 4-338,372), and the like.
- the objective of the present invention is to provide a novel condensed heterocyclic derivative exhibiting an excellent anti-fungal activity.
- the present inventors have synthesized various condensed heterocyclic derivatives and have carried out extensive research in connection with their effects on the physiological activities of fungi. As a result, we have found that the compounds according to the present invention exhibit a broad spectrum of anti-fungal activity especially against downy mildew and late blight, and at the same time they do not harm the useful plant growth.
- a condensed heterocyclic derivative represented by formula [I]: ##STR2## wherein R 1 represents a lower alkyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a cyano group, and a methoxy group, an alkenyl group, an alkynyl group, a cycloalkyl group optionally having at least one methyl group, a cycloalkenyl group optionally having at least one methyl group, a cyclic ether group optionally having at least one methyl group, an aralkyl group optionally having at least one substituent selected from the group consisting of a methyl group, a methoxy group, and a nitro group, a phenyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a methyl group, a methoxy group, a nitro group, and a methoxycarbon
- R 2 , R 3 , R 4 , R 5 , and R 6 independently represent a hydrogen atom, a lower alkyl group optionally having at least one halogen group, a cycloalkyl group, an aralkyl group; a phenyl group, a cyano group, an acyl group, a lower alkoxy group, or a lower alkoxycarbonyl group,
- R 2 may form an alkylic ring having 3 to 6 carbon atoms with R 3 ;
- Z is represented by the following formulae: ##STR3## wherein X represents a hydrogen atom, a halogen atom, an alkyl group optionally having at least one halogen atom, an alkynyl group, a methoxy group, a trifluoromethoxy group, a hydroxyl group, a methoxycarbonyl group, a methylcarbonyloxy group, an amino group, a dimethylamino group, a nitro group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group, a phenyl group, an acetyl group, a formyl group, or a cyano group;
- n is an integer of 1, 2, or 3;
- A is O, S, N, or represented by the formula: ##STR4## wherein R 7 represents a hydrogen atom, a methyl group, an acetyl group, or a benzoyl group; and
- W is represented by --C(O)--, --SO 2 --, --NHC(O)--, --N(CH 3 )C(O)--, --OC(O)--, --SC(O)--, --OC(S)--, or --SC(S)--.
- an agricultural or horticultural fungicide containing the condensed heterocyclic derivative described above as the active ingredient is provided.
- alkyl group is used herein to mean a straight or branched alkyl group possessing 1 to 15 carbon atoms including, but not limited to, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1 -dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group,
- a lower alkyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a cyano group, and a methoxy group includes, for example, a monochloroethyl group, trifluoroethyl group, 1-cyanoethyl group, 1-cyano-1-methylethyl group, 1-methoxy-1-trifluoromethylbutyl group, perfluoro-tert-butyl group or the like.
- halogen is used herein to mean a fluorine atom, chlorine atom, bromine atom, iodine atom, or the like.
- alkenyl group is used herein to mean a straight or branched alkenyl group possessing 2 to 6 carbon atoms and including, but not limited to, a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1-propenyl group, 2-methylpropenyl group, 1-ethylvinyl group, 2-pentenyl group, 2-hexenyl group, or the like.
- alkynyl group is used herein to mean a straight or branched alkynyl group possessing 2 to 6 carbon atoms and including, for example, an ethynyl group, propynyl group, butynyl group, 1-methyl-2-propynyl group, 2-pentynyl group, 2-hexynyl or the like.
- cycloalkyl group is used herein to mean a cycloalkyl group possessing 3 to 8 carbon atoms and including, but not limited to, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, or the like.
- a cycloalkyl group optionally having at least one methyl group includes, for example, a 1-methylcyclopropyl group, 2-methylcyclopropyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1,2-dimethylcyclopentyl group, 1,2,3-trimethylcyclopentyl group, or the like.
- cycloalkenyl is used herein to mean a cycloalkenyl group possessing 3 to 8 carbon atoms and including, but not limited to, a 1-cyclopropenyl group, 2-cyclopropenyl group, 1-cyclobutenyl group, 2-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group, 4-cycloheptenyl group, 1-cyclooctenyl group, 2-cyclooctenyl group, 3-cyclooctenyl group, 4-cyclooctenyl group, or the like.
- a cycloalkenyl group optionally having at least one methyl group includes, for example, a 1-methyl-2-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 3 -methyl-1-cyclopentenyl group, 3,4-dimethyl-1-cyclopentenyl group, 1-methyl-2-cyclohexenyl group, 4-methyl-1-cyclohexenyl group, 1,2,5-trimethyl-3-cyclohexenyl group, or the like.
- aralkyl is used herein to mean an aralkyl group possessing 7 to 10 carbon atoms and including, but not limited to, a benzyl group, phenethyl group, or the like.
- An aralkyl group optionally having at least one substituent selected from the group consisting of a methyl group, a methoxy group, and a nitro group includes, for example, a 4-methylbenzyl group, ⁇ -methylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dimethylbenzyl group, 2-methyl-3-methoxy-4-nitrobenzyl group, ⁇ -methyl-4-methylphenethyl group or the like.
- cyclic ether group is used herein to mean a cyclic ether group possessing 2 to 6 carbon atoms and including, for example, an oxiranyl group, 2-oxetanyl group, 3-tetrahydrofuryl group, 2-tetrahydropyranyl group, or the like.
- a cyclic ether group optionally having at least one methyl group includes, for example, 2-methyloxiranyl, 2-methyl-3-tetrahydrofuryl group, 2,4-dimethyl-3-tetrahydrofuryl group, 2,4,5-trimethyl-3-tetrahydrofuryl group, or the like.
- An acyl group includes an acetyl group, benzoyl group, or the like.
- a phenyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a methyl group, a methoxy group, a nitro group, and a methoxycarbonyl group includes, for example, a 2-chlorophenyl group, 3-methylphenyl group, 4-methoxyphenyl group, 4-nitrophenyl group, 4-methoxycarbonylphenyl group, 2-methoxy-4-nitrophenyl group, perfluorophenyl group or the like.
- the preferred compounds of this invention consist of the compounds represented by formula (I), wherein R 1 represents a straight or branched alkyl group possessing 2 to 6 carbon atoms, a straight or branched alkenyl group possessing 3 carbon atoms, a cycloalkyl group possessing 5 to 6 carbon atoms, or a non-substituted phenyl group; R 2 represents a hydrogen atom; R 3 represents an isopropyl group; R 4 represents a hydrogen atom, a phenyl group, a methyl group, or an ethyl group; R 5 represents a hydrogen atom or a methyl group; R 6 represents a hydrogen atom; W is represented by --OC(O)--; Z represents a substituted heterocyclic group including a benzofuran group, a benzothiophene group, an indole group, a 2,3-dihydrobenzofuran group having one or two (same or different) substituent such as a hydrogen
- the compounds represented by formula [I] according to the present invention can exist in stereoisomers by venue of the presence of two or more chiral centers.
- the present invention contemplate all such stereoisomers, including diastereomers, enantiomers, and mixtures thereof, which can be separated by appropriate methods.
- Compound Nos. 132 and 133 are a mixture of diastereomers, and are also one of the individual diastereomers, respectively.
- Compound Nos. 161 and 162 are the individual diastereomers. ##STR5##
- the compounds represented by formula [I] according to the present invention can be prepared by reacting an amino acid derivative represented by formula [II] or the amino acid derivative wherein the carboxyl group is activated, with an amine represented by formula [III] in the presence of a base and/or a catalyst if necessary.
- amino acid derivative represented by formula [II] with an activated carboxyl group there can be mentioned, for example, an acid halide such as an acid chloride, an acid anhydride derived from the two molecules of the amino acid derivatives represented by formula [II], a mixed acid anhydride derived from the amino acid derivative represented by formula [II] and other acid or an O-alkyl carbonic acid, and an activated ester such as p-nitrophenyl ester, 2-tetrahydropyranyl ester, and 2-pyridyl ester and the like.
- an acid halide such as an acid chloride
- an acid anhydride derived from the two molecules of the amino acid derivatives represented by formula [II] a mixed acid anhydride derived from the amino acid derivative represented by formula [II] and other acid or an O-alkyl carbonic acid
- an activated ester such as p-nitrophenyl ester, 2-tetrahydropyranyl ester, and 2-pyridyl ester and
- this solvent can be any solvent that does not hinder the reaction, for example, hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene and the like, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like, ethers such as diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and the like, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and the like, esters such as methyl acetate, ethyl acetate and the like, nit
- the base can be any type of base generally used in this type of reaction.
- hydroxides of alkaline metals such as sodium hydroxide, potassium hydroxide and the like
- hydroxides of alkaline earth metals such as calcium hydroxide and the like
- carbonates of alkaline metals such as potassium carbonate and the like
- organic bases such as triethylamine, trimethylamine, dimethylaniline, pyridine, N-methylpiperidine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazadicyclo[5.4.0]undec-7-ene (DBU), and the like
- tertiary amines such as triethylamine, pyridine, N-methylpiperidine and the like.
- the catalyst there can be mentioned 4-dimethylaminopyridine, 1hydroxybenzotriazole, dimethylformamide and the like.
- the present reaction is carried out at a temperature of -75° C. to 100° C., preferably -60° C. to 40%.
- the reaction time is preferably 1 to 20 hours.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , W, and Z represent the same meanings as stated above, and Y represents a halogen atom, an R 1 OC(O)O-- group or a R 1 C(O)O-- group.
- Compounds represented by formula [I] of the present invention can be manufactured by means of reacting the compound represented by formula [IV] with an amine represented by formula [V], a salt of the amine derivative with an inorganic acid such as hydrochloride and the like, or a salt of the amine derivative with an organic acid such as tosylate and the like, in the presence of a base when required.
- this solvent can be any solvent that does not hinder the reaction, for example, hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene and the like, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like, ethers such as diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and the like, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and the like, esters such as methyl acetate, ethyl acetate and the like, nit
- the base can be any type of base generally used in this type of reaction.
- hydroxides of alkaline metals such as sodium hydroxide, potassium hydroxide and the like, hydroxides of alkaline earth metals such as calcium hydroxide and the like, carbonates of alkaline metals such as potassium carbonate and the like, organic bases such as triethylamine, trimethylamine, dimethylaniline, N-methylmorpholine, pyridine, N-methylpiperidine, 1,5-diazadicyclo [4.3.0]non-5-ene (DBN), 1,8-diazadicyclo [5.4.0]undec-7-ene (DBU), and the like, and preferably tertiary amines such as triethylamine, pyridine, N-methylpiperidine and the like.
- the present reaction is carried out at a temperature of -20° C. to 100° C., preferably 0° C. to 40° C.
- the reaction time is preferably 30 minutes to 20 hours.
- Compounds represented by formula [V] as the starting material represent novel compounds, and can be manufactured, for example, by means of treating carbamates of compounds [I] synthesized by the procedure of preparation process A using a conventional process for removing the amino protecting group of the amino acid such as catalytic reduction, or by treating with acids such as liquid hydrofluoric acid, sulfonic acids, hydrochloric acid, hydrobromic acid, formic acid and the like.
- the mixture was then allowed to cool to room temperature, after which 10% hydrochloric acid was added, adjusting the mixture to a pH of 3-4.
- the resultant water layer was made basic with an aqueous solution of sodium hydroxide and extracted with 200 ml of ether.
- the organic layer was washed with water and dried over anhydrous magnesium sulfate.
- N-methylpiperidine 0.4 g was added to a solution containing 0.8 g of N-tert-butoxycarbonyl-L-valine dissolved in 40 ml of dichloromethane, at -20° C. or lower. After the mixture was stirred for 10 minutes at the same temperature, 0.5 g of isobutyl chloroformate was added to the mixture at -40° C., and stirred for 1 hour between -40° C. and -15° C. 0.7 g of 1-(5-cyano-2-benzofuranyl)ethylamine was added to this mixture at -20° C., and then the reaction mixture was allowed to sit and warm naturally to room temperature, with stirring. Water was subsequently added to the reaction mixture.
- N-methylpiperidine 0.5 g was added to a solution containing 1.3 g of N-tert-butoxycarbonyl-L-valine dissolved in 25 ml of dichloromethane, at -20° C. or lower.
- the reaction mixture was stirred at the same temperature for 10 minutes.
- 0.7 g of isobutyl chloroformate was added to the mixture at -40° C. and then stirred between -40° C. and -15° C. for 1 hour.
- 1.0 g of 1-[3-methyl-2-benzo[b]thienyl]ethylamine was added to the mixture at -20° C. The mixture was allowed to sit and warm naturally to room temperature with stirring. Water was subsequently added to the reaction mixture.
- N-methylpiperidine was added to a solution containing 3.1 g of N-tert-butoxycarbonyl-L-valine dissolved in 80 ml of dichloromethane, at -20° C. or lower and then the mixture was stirred at the same temperature for 10 minutes.
- 2.0 g of isobutyl chloroformate was added to the mixture at -40° C. and the entire mixture was stirred between -40° C. and -15° C. for 1 hour.
- 2.5 g of 1-(3-methyl-2-indolyl)ethylamine was then added to the mixture at -20° C. The mixture was allowed to sit and warm naturally to room temperature and then stirred for 12 hours at room temperature. Water was subsequently added to the reaction mixture.
- N-methylpiperidine was added to a solution containing 1.5 g of N-tert-butoxycarbonyl-L-valine dissolved in 50 ml of dichloromethane, at -20° C. or lower and then the mixture was stirred at the same temperature for 10 minutes.
- 0.9 g of isobutyl chloroformate was added to the mixture at -40° C. and the entire mixture was stirred at -40° C.--15° C. for 1 hour.
- 1.1 g of 1-(3-indolyl)ethylamine was added to the mixture at -20° C. The mixture was allowed to sit and warm naturally to room temperature and then stirred at room temperature for 12 hours. Water was subsequently added to the reaction mixture.
- the agricultural or horticultural fungicide according to the present invention is a composition containing a condensed heterocyclic derivative represented by formula [I] as an active ingredient.
- the compounds acting as the active ingredient can be formulated appropriately, depending on the purpose.
- the active ingredient is usually diluted in an inert liquid or a solid carder, and a surfactant, a dispersant, an adjuvant, and the like are added thereto if necessary.
- the mixture is then formulated in a known manner into, for example, a fine powder, a wettable powder, an emulsifiable concentrate, granules, or the like.
- carders employed in the formulation are solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermicuIite, slaked lime, siliceous sand, ammonium sulfate, urea, or the like; and liquid carders such as isopropyl alcohol, xylene, cyclohexanone, methylnaphthalene, and the like.
- Illustrative examples of the surfactants and dispersants include salts of dinaphthylmethanesulfonic acid, alkylarylsulfonic acid, and ligninesulfonic acid, sulfate esters of alcohol, polyoxyethylene glycol ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylenesorbitan monoalkylates, and the like.
- Suitable examples of auxiliary agents include carboxymethylcellulose, and the like.
- the agricultural or horticultural fungicide according to the present invention can be employed for a number of purposes: for example, treating seeds, spraying of stem and leaf portions, injection into the applying water, and applying into the soil.
- the proportion of the active ingredient is selected as needed. When formulated into a fine powder or granules, 0.1% by weight to 20% by weight of the active ingredient is preferred. For an emulsifiable concentrate or wettable powder, 5% by weight to 80% by weight of the active ingredient is adequate.
- the rate of application of the agricultural or horticultural fungicide according to the present invention may vary depending on the type of active compound employed, the kind of the pest or disease to be controlled, the nature of occurrence of the pest or disease, the degree of damage, environmental conditions, the form of preparation to be used, and the like.
- the rate of application of the active ingredient be suitably chosen within the range of 0.1 g to 5 kg per 10 ares, preferably, in the range of 1 g to 1 kg per 10 ares.
- the fungicide of the present invention is in the form of a liquid such as an emulsifiable concentrate or a wettable powder
- the ratio for application of the active ingredient be suitably chosen within the range of 0.1 ppm to 10,000 ppm, and preferably within the range of 10 ppm to 3,000 ppm.
- the compounds according to the present invention in the formulation described above can control plant diseases caused by fungi belonging to Oomycetes, Ascomycetes, Deuteromycetes, and Basidiomycetes or other pathogenic fungi.
- the fungi include, but are not limited to, Pseudoperonospora such as cucumber downy mildew (Pseudoperonospora cubensis), Phytophthora such as tomato late blight (Phytophthora infestans), and Plasmopara such as grape downy mildew (Plasmopara viticola).
- the agricultural or horticultural fungicide according to the present invention may be employed alone or in combination with other fungicides, insecticides, herbicides, plant growth modifiers, fertilizers or the like.
- the agricultural or horticultural fungicides according to the present invention exhibit high ability to control the growth or spread of cucumber downy mildew (Pseudoperonospora cubensis), tomato late blight (Phytophthora infestans), and grape downy mildew (Plasmopara viticola), and are effective for potato late blight (Phytophthora infestans).
- the agricultural or horticultural fungicides according to the present invention not only exhibit the ability to present fungal infection, but also exhibit the ability to eliminate pathogenic fungi after it has invaded a host plant.
- the agricultural or horticultural fungicides of the present invention are also characterized in that they are not harmful chemicals and exhibit excellent characteristics such as systemic action, residual activity, and the influence of rain-fall on effect.
- Cucumber seeds (variety: "Sagami hanjiro") were sown at a rate of 10 seeds each in a square PVC(polyvinyl chloride) pot, wherein each side is 9 cm wide. The seeds were allowed to grow in a greenhouse, for 7 days, to the cotyledonous stage.
- a wettable powder prepared as in Formulation Example 2 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then applied at a rate of 10 ml per pot to the cucumber seedlings at their cotyledonous stage.
- Class B Incidence area is less than 25%.
- Class C Incidence area is 25% or more and less than 50%.
- Class D Incidence area is 50% or more.
- Cucumber seeds (variety: "Sagami hanjiro") were sown at a rate of 10 seeds each in a square PVC (polyvinyl chloride) pot, wherein each side is 9 cm wide. The seeds were allowed to grow in a greenhouse, for 7 days, to the cotyledonous stage. The seedlings were inoculated with a spore suspension of cucumber downy mildew (Pseudoperonospora cubensis) fungi and then placed in a moist chamber at 22° C. for 24 hours.
- cucumber downy mildew Pieris
- a wettable powder prepared as in Formulation Example 2 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then applied at a rate of 10 ml per pot to the cucumber seedlings. The seedlings were then placed in a green house. On the seventh day after the inoculation, the extent of lesion was rated in accordance with the following standards of evaluation in order to secure the effect of treating with the compounds according to the present invention. The same Comparative Compounds as disclosed in Test Example 1 were employed. The results of the test are given in Table 12.
- Class B Incidence area is less than 25%.
- Class C Incidence area is 25% or more and less than 50%.
- Class D Incidence area is 50% or more.
- Incidence Index 1 Incidence area is less than 5%
- Incidence Index 2 Incidence area is 5% or more and less than 33.3%
- Incidence Index 3 Incidence area is 33.3% or more and less than 66.6%
- Incidence Index 4 Incidence area is 66.6% or more ##EQU1##
- One grape seedling (variety: "Kyoho") each was grown by cutting and pruned in a porcelain pot (diameter: 12 cm) and maintained in a greenhouse.
- a wettable powder prepared as in Formulation Example 2 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then applied at a rate of 20 ml per pot to the grape seedlings at their 4- or 5-leaf stage. After drying in the air, the plant was inoculated with a zoosporangium suspension of grape downy mildew (Plasmopara viticola) fungi and then placed in a moist chamber at 22° C. for 24 hours.
- grape downy mildew Pusmopara viticola
- Incidence Index 1 Incidence area is less than 5%
- Incidence Index 2 Incidence area is 5% or more and less than 33.3%
- Incidence Index 3 Incidence area is 33.3% or more and less than 66.6%
- Incidence Index 4 Incidence area is 66.6% or more
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Plural Heterocyclic Compounds (AREA)
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Quinoline Compounds (AREA)
- Pyrane Compounds (AREA)
- Indole Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Abstract
The present invention provides a condensed heterocyclic derivative represented by a formula: <IMAGE> wherein R1 represents a lower alkyl group, an alkenyl group, or the like, R2, R3, R4, R5, and R6 independently represent a hydrogen atom, a lower alkyl, or the like, W is represented by -OC(O)-, -SC(O)-, or the like, and Z represents a 2-indolyl group or the like. The present invention also provides an agricultural or horticultural fungicide which comprises an amount of the condensed derivative known to be effective as a fungicide. The agricultural or horticultural fungicide according to the present invention exhibits a superior control effect for downy mildew and late blight, without harm to nonfungal, photosynthesizing plants.
Description
The present invention relates to a condensed heterocyclic derivative as well as an agricultural or horticultural fungicide containing the same as an active ingredient. The present invention also relates to a process for preparing the condensed heterocyclic derivative.
Heretofore, some aminoacid amide derivatives have been known as a pesticide and also as a herbicide. For instance, such aminoacid amide derivatives include N-(tert-butoxycarbonyl)-L-valine-4-methoxyphenylethylamide (Japanese Patent Application First Publication No. Hei 3-5,451), N2 -phenoxycarbonyl-N1 -[racemi-1-(4-chlorophenyl)ethyl]-L-isoleucinamide (Japanese Patent Application First Publication No. Hei 3-153,657), N-(isopropyl-oxycarbonyl)-L-valine-4-methoxyphenylethylamide (Japanese Patent Application First Publication No. Hei 4-230,652), N2 -phenoxycarbonyl-N1 -[racemi-1-(4-chlorophenyl)ethyl]-L-cyclopentylglycine (Japanese Patent Application First Publication No. Hei 4-230,653), N2 -sec-butyloxycarbonyl-N1 -[S(+)-1-cyclohexylethyl]-L-valinamide (Japanese Patent Application First Publication No. Hei 4-283,554), benzyl {(D,L)-1-[(3,4-dimethoxyphenethyl)carbamoyl]-n-butyl}carbamate (Japanese Patent Application First Publication No. Hei 4-308,507), N-(i-propyloxycarbonyl)-L-valine-diphenylmethylamide (Japanese Patent Application First Publication No. Hei 4-338,372), and the like.
These conventional compounds, however, do not have sufficient effect to act as a pesticide. In addition, the prior an documents do not disclose an amino-acid amide derivative possessing a condensed heterocyclic ring such as a benzofuran ring, benzothiophene ring, or the like. Therefore, the utility of the aminoacid amide derivatives has not been known.
The objective of the present invention is to provide a novel condensed heterocyclic derivative exhibiting an excellent anti-fungal activity.
The present inventors have synthesized various condensed heterocyclic derivatives and have carried out extensive research in connection with their effects on the physiological activities of fungi. As a result, we have found that the compounds according to the present invention exhibit a broad spectrum of anti-fungal activity especially against downy mildew and late blight, and at the same time they do not harm the useful plant growth.
According to a first aspect of the present invention, there is provided a condensed heterocyclic derivative represented by formula [I]: ##STR2## wherein R1 represents a lower alkyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a cyano group, and a methoxy group, an alkenyl group, an alkynyl group, a cycloalkyl group optionally having at least one methyl group, a cycloalkenyl group optionally having at least one methyl group, a cyclic ether group optionally having at least one methyl group, an aralkyl group optionally having at least one substituent selected from the group consisting of a methyl group, a methoxy group, and a nitro group, a phenyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a methyl group, a methoxy group, a nitro group, and a methoxycarbonyl group, a dimethylamino group, or an ethoxy carbonyl group,
R2, R3, R4, R5, and R6 independently represent a hydrogen atom, a lower alkyl group optionally having at least one halogen group, a cycloalkyl group, an aralkyl group; a phenyl group, a cyano group, an acyl group, a lower alkoxy group, or a lower alkoxycarbonyl group,
R2 may form an alkylic ring having 3 to 6 carbon atoms with R3 ;
Z is represented by the following formulae: ##STR3## wherein X represents a hydrogen atom, a halogen atom, an alkyl group optionally having at least one halogen atom, an alkynyl group, a methoxy group, a trifluoromethoxy group, a hydroxyl group, a methoxycarbonyl group, a methylcarbonyloxy group, an amino group, a dimethylamino group, a nitro group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group, a phenyl group, an acetyl group, a formyl group, or a cyano group;
n is an integer of 1, 2, or 3;
A is O, S, N, or represented by the formula: ##STR4## wherein R7 represents a hydrogen atom, a methyl group, an acetyl group, or a benzoyl group; and
W is represented by --C(O)--, --SO2 --, --NHC(O)--, --N(CH3)C(O)--, --OC(O)--, --SC(O)--, --OC(S)--, or --SC(S)--.
According to a second aspect of the present invention, there is provided an agricultural or horticultural fungicide containing the condensed heterocyclic derivative described above as the active ingredient.
In the present specification, the term "lower" is used herein to mean possessing at most 6 carbon atoms. The term "alkyl group" is used herein to mean a straight or branched alkyl group possessing 1 to 15 carbon atoms including, but not limited to, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1 -dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, or the like.
A lower alkyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a cyano group, and a methoxy group includes, for example, a monochloroethyl group, trifluoroethyl group, 1-cyanoethyl group, 1-cyano-1-methylethyl group, 1-methoxy-1-trifluoromethylbutyl group, perfluoro-tert-butyl group or the like.
The term "halogen" is used herein to mean a fluorine atom, chlorine atom, bromine atom, iodine atom, or the like. The term "alkenyl group" is used herein to mean a straight or branched alkenyl group possessing 2 to 6 carbon atoms and including, but not limited to, a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1-propenyl group, 2-methylpropenyl group, 1-ethylvinyl group, 2-pentenyl group, 2-hexenyl group, or the like. The term "alkynyl group" is used herein to mean a straight or branched alkynyl group possessing 2 to 6 carbon atoms and including, for example, an ethynyl group, propynyl group, butynyl group, 1-methyl-2-propynyl group, 2-pentynyl group, 2-hexynyl or the like.
The term "cycloalkyl group" is used herein to mean a cycloalkyl group possessing 3 to 8 carbon atoms and including, but not limited to, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, or the like.
A cycloalkyl group optionally having at least one methyl group includes, for example, a 1-methylcyclopropyl group, 2-methylcyclopropyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1,2-dimethylcyclopentyl group, 1,2,3-trimethylcyclopentyl group, or the like.
The term "cycloalkenyl" is used herein to mean a cycloalkenyl group possessing 3 to 8 carbon atoms and including, but not limited to, a 1-cyclopropenyl group, 2-cyclopropenyl group, 1-cyclobutenyl group, 2-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group, 4-cycloheptenyl group, 1-cyclooctenyl group, 2-cyclooctenyl group, 3-cyclooctenyl group, 4-cyclooctenyl group, or the like.
A cycloalkenyl group optionally having at least one methyl group includes, for example, a 1-methyl-2-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 3 -methyl-1-cyclopentenyl group, 3,4-dimethyl-1-cyclopentenyl group, 1-methyl-2-cyclohexenyl group, 4-methyl-1-cyclohexenyl group, 1,2,5-trimethyl-3-cyclohexenyl group, or the like.
The term "aralkyl" is used herein to mean an aralkyl group possessing 7 to 10 carbon atoms and including, but not limited to, a benzyl group, phenethyl group, or the like.
An aralkyl group optionally having at least one substituent selected from the group consisting of a methyl group, a methoxy group, and a nitro group, includes, for example, a 4-methylbenzyl group, α-methylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dimethylbenzyl group, 2-methyl-3-methoxy-4-nitrobenzyl group, α-methyl-4-methylphenethyl group or the like.
The term "cyclic ether group" is used herein to mean a cyclic ether group possessing 2 to 6 carbon atoms and including, for example, an oxiranyl group, 2-oxetanyl group, 3-tetrahydrofuryl group, 2-tetrahydropyranyl group, or the like.
A cyclic ether group optionally having at least one methyl group includes, for example, 2-methyloxiranyl, 2-methyl-3-tetrahydrofuryl group, 2,4-dimethyl-3-tetrahydrofuryl group, 2,4,5-trimethyl-3-tetrahydrofuryl group, or the like.
An acyl group includes an acetyl group, benzoyl group, or the like.
A phenyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a methyl group, a methoxy group, a nitro group, and a methoxycarbonyl group includes, for example, a 2-chlorophenyl group, 3-methylphenyl group, 4-methoxyphenyl group, 4-nitrophenyl group, 4-methoxycarbonylphenyl group, 2-methoxy-4-nitrophenyl group, perfluorophenyl group or the like.
The preferred compounds of this invention consist of the compounds represented by formula (I), wherein R1 represents a straight or branched alkyl group possessing 2 to 6 carbon atoms, a straight or branched alkenyl group possessing 3 carbon atoms, a cycloalkyl group possessing 5 to 6 carbon atoms, or a non-substituted phenyl group; R2 represents a hydrogen atom; R3 represents an isopropyl group; R4 represents a hydrogen atom, a phenyl group, a methyl group, or an ethyl group; R5 represents a hydrogen atom or a methyl group; R6 represents a hydrogen atom; W is represented by --OC(O)--; Z represents a substituted heterocyclic group including a benzofuran group, a benzothiophene group, an indole group, a 2,3-dihydrobenzofuran group having one or two (same or different) substituent such as a hydrogen atom, a fluorine atom, a chlorine atom, a nitro group, a cyano group, or a methyl group; and the amino acid is an L-isomer.
The compounds represented by formula [I] according to the present invention can exist in stereoisomers by venue of the presence of two or more chiral centers. The present invention contemplate all such stereoisomers, including diastereomers, enantiomers, and mixtures thereof, which can be separated by appropriate methods.
Next, the compounds represented by formula [I] according to the present invention are listed in Tables 1 to 7. However, it should be understood that the invention is not limited to these compounds. The compound Nos. given in Tables 1 to 7 will be referred to in the subsequent description.
In Tables 1 to 7, Compound Nos. 1, 2, and 3; Compound Nos. 68, 69, and 303; Compound Nos. 70, 71, and 296; Compound Nos. 129, 130, and 131; Compound Nos. 136, 137, and 138; Compound Nos. 108, 375, and 109; Compound Nos. 382, 23, and 24; Compound Nos. 376, 163, and 164; and Compound Nos. 377, 378, and 379 are a mixture of diastereomers, and are also individual diastereomers. In addition, Compound Nos. 16 and 17; Compound Nos. 97 and 98; Compound Nos. 102 and 103; Compound Nos. 115 and 327; Compound Nos. 132 and 133; Compound Nos. 227 and 362; Compound Nos. 228 and 364; Compound Nos. 230 and 365; Compound Nos. 233 and 363; Compound Nos. 336 and 337; Compound Nos. 405 and 406; and Compound Nos. 423 and 424 are a mixture of diastereomers, and are also one of the individual diastereomers, respectively. Compound Nos. 161 and 162 are the individual diastereomers. ##STR5##
TABLE 2
__________________________________________________________________________
Melting Point
Com- Amino
(°C.) or
pound Acid
Refractive
No. R.sup.1 R.sup.2
R.sup.3
R.sup.4
R.sup.5
W Xn A Isomer
Index (n.sub.D.sup.20)
__________________________________________________________________________
387 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H O L 144-148
388 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H O L 159-164
389 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-CH.sub.3
O L not determined
390 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H S L
391 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H S L
392
##STR6## H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H S L
393 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-Cl
O L 58-60
394 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-NO.sub.2
O L
395 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-Cl
O L 132-135
396 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-NO.sub.2
O L
397
##STR7## H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-CN
O L not determined
398 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-CN
O L not determined
399
##STR8## H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-Cl
O L 134- 139
400
##STR9## H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-F O L 126-130
401 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-F O L 160-163
402
##STR10##
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-F O L not determined
403 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
5-F O L <30
404 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H NCH.sub.3
L 99-103
__________________________________________________________________________
TABLE 3
__________________________________________________________________________
##STR11##
Melting Point
Com- Amino
(°C.) or
pound Acid
Refractive
No. R.sup.1
R.sup.2
R.sup.3
R.sup.4
R.sup.5
W Xn
A Isomer
Index (n.sub.D.sup.20)
__________________________________________________________________________
405 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H NH L 83-86
406 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H NH L 89-94
407 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H NCH.sub.3
L 128-130
408 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H O L
409 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H S L
__________________________________________________________________________
TABLE 4
__________________________________________________________________________
##STR12##
Melting Point
Com- Amino
(°C.) or
pound Acid
Refractive
No. R.sup.1
R.sup.2
R.sup.3
R.sup.4
R.sup.6
Xn A Isomer
Index (n.sub.D.sup.20)
__________________________________________________________________________
410 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
H O L
411 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
H O L
412
##STR13##
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
H O L
413 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
5-Cl
O L 44-46
414 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
5-Cl
O L 68-69
415
##STR14##
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
5-Cl
O L
416 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
5-NO.sub.2
O L
417 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
H S L 162-165
418 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
H S L
419 t-C.sub.4 H.sub.9
CH.sub.3
i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
H O DL
420 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
C.sub.2 H.sub.5
H O L
421 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
i-C.sub.3 H.sub.7
H O L
422 sec-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
CH.sub.3
5-Cl
O L
__________________________________________________________________________
TABLE 5
__________________________________________________________________________
##STR15##
Melting Point
Com- Amino
(°C.) or
pound Acid
Refractive
No. R.sup.1
R.sup.2
R.sup.3
R.sup.4
R.sup.5
W Xn
A Isomer
Index (n.sub.D.sup.20)
__________________________________________________________________________
423 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H N L 178-182
424 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H N L 124-127
425 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H N L 186-190
426
##STR16##
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H N L 151-154
__________________________________________________________________________
TABLE 6
__________________________________________________________________________
##STR17##
Melting Point
Com- Amino
(°C.) or
pound Acid
Refractive
No. R.sup.1
R.sup.2
R.sup.3
R.sup.4
R.sup.5
W Xn
A Isomer
Index (n.sub.D.sup.20)
__________________________________________________________________________
427 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H NH L not determined
428 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H NCH.sub.3
L 160-162
429 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H NH L
430
##STR18##
H i-C.sub.3 H.sub.7
CH.sub. 3
H OC(O)
H NH L
__________________________________________________________________________
TABLE 7
__________________________________________________________________________
##STR19##
Melting Point
Com- Amino
(°C.) or
pound Acid
Refractive
No. R.sup.1
R.sup.2
R.sup.3
R.sup.4
R.sup.5
W Xn
A Isomer
Index (n.sub.D.sup.20)
__________________________________________________________________________
431 t-C.sub.4 H.sub.9
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H O L
432 i-C.sub.3 H.sub.7
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H O L not determined
433
##STR20##
H i-C.sub.3 H.sub.7
CH.sub.3
H OC(O)
H O L
__________________________________________________________________________
The compounds represented by formula [I] according to the present invention can be prepared in the following manner. ##STR21## wherein R1, R2, R3, R4, R5, R6, W and Z ,are the same as described above.
The compounds represented by formula [I] according to the present invention can be prepared by reacting an amino acid derivative represented by formula [II] or the amino acid derivative wherein the carboxyl group is activated, with an amine represented by formula [III] in the presence of a base and/or a catalyst if necessary.
In the present reaction, as the amino acid derivative represented by formula [II] with an activated carboxyl group there can be mentioned, for example, an acid halide such as an acid chloride, an acid anhydride derived from the two molecules of the amino acid derivatives represented by formula [II], a mixed acid anhydride derived from the amino acid derivative represented by formula [II] and other acid or an O-alkyl carbonic acid, and an activated ester such as p-nitrophenyl ester, 2-tetrahydropyranyl ester, and 2-pyridyl ester and the like. These compounds can be synthesized according to conventional methods [for example, see Methoden der Organischen Chemie, Vol. 15, No. 2, from page 2; Georg Thieme Verlag Stuttgart: 1974; Chemische Berichte, Vol. 38, page 605 (1905); Journal of the American Chemical Society, Vol. 74. page 676 (1952); and Journal of the American Chemical Society, Vol. 86, page 1839 (1964)].
In addition, it is also possible to perform the present reaction using a condensing agent such as N, N'-dicyclohexylcarbodiimide, carbonyldiimidazole or the like.
The present reaction can be performed in a conventional solvent: this solvent can be any solvent that does not hinder the reaction, for example, hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene and the like, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like, ethers such as diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and the like, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and the like, esters such as methyl acetate, ethyl acetate and the like, nitriles such as acetonitrile, propionitrile, benzonitrile and the like, aprotic solvents such as dimethylsulfoxide, dimethylformamide, sulfolane and the like, and mixed solvents combining solvents selected from the aforementioned.
The base can be any type of base generally used in this type of reaction. For example, there can be mentioned hydroxides of alkaline metals such as sodium hydroxide, potassium hydroxide and the like, hydroxides of alkaline earth metals such as calcium hydroxide and the like, carbonates of alkaline metals such as potassium carbonate and the like, organic bases such as triethylamine, trimethylamine, dimethylaniline, pyridine, N-methylpiperidine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazadicyclo[5.4.0]undec-7-ene (DBU), and the like, and preferably tertiary amines such as triethylamine, pyridine, N-methylpiperidine and the like.
As the catalyst there can be mentioned 4-dimethylaminopyridine, 1hydroxybenzotriazole, dimethylformamide and the like. The present reaction is carried out at a temperature of -75° C. to 100° C., preferably -60° C. to 40%. The reaction time is preferably 1 to 20 hours.
Furthermore, compounds represented by formula [II] as the starting material are known and can generally be synthesized by conventional methods [for example, see Methoden der Organischen Chemie, Vol. 15, No. 2, from page 2; Georg Thieme Verlag Stuttgart: 1974; Chemistry of the Amino Acids, vol. 2, page 891; John Wiley & Sons, N.Y.( 1964); and Journal of the American Chemical Society, Vol. 79, page 4686 (1957)]. Various manufacturing methods for compounds [III] can also be considered such as those methods stated in Japanese patent application, First Publication No. Sho 63-146876 and Synthesis, page 24, 1978). The majority of compounds [III] represent novel compounds. ##STR22## wherein R1, R2, R3, R4, R5, R6, W, and Z represent the same meanings as stated above, and Y represents a halogen atom, an R1 OC(O)O-- group or a R1 C(O)O-- group.
Compounds represented by formula [I] of the present invention can be manufactured by means of reacting the compound represented by formula [IV] with an amine represented by formula [V], a salt of the amine derivative with an inorganic acid such as hydrochloride and the like, or a salt of the amine derivative with an organic acid such as tosylate and the like, in the presence of a base when required.
The present reaction can be performed in a conventional solvent: this solvent can be any solvent that does not hinder the reaction, for example, hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene and the like, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like, ethers such as diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and the like, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and the like, esters such as methyl acetate, ethyl acetate and the like, nitriles such as acetonitrile, propionitrile, benzonitrile and the like, aprotic solvents such as dimethylsulfoxide, dimethylformamide, sulfolane and the like, water, and mixed solvents combining solvents selected from the aforementioned.
The base can be any type of base generally used in this type of reaction. For example, there can be mentioned hydroxides of alkaline metals such as sodium hydroxide, potassium hydroxide and the like, hydroxides of alkaline earth metals such as calcium hydroxide and the like, carbonates of alkaline metals such as potassium carbonate and the like, organic bases such as triethylamine, trimethylamine, dimethylaniline, N-methylmorpholine, pyridine, N-methylpiperidine, 1,5-diazadicyclo [4.3.0]non-5-ene (DBN), 1,8-diazadicyclo [5.4.0]undec-7-ene (DBU), and the like, and preferably tertiary amines such as triethylamine, pyridine, N-methylpiperidine and the like. The present reaction is carried out at a temperature of -20° C. to 100° C., preferably 0° C. to 40° C. The reaction time is preferably 30 minutes to 20 hours.
Compounds represented by formula [V] as the starting material represent novel compounds, and can be manufactured, for example, by means of treating carbamates of compounds [I] synthesized by the procedure of preparation process A using a conventional process for removing the amino protecting group of the amino acid such as catalytic reduction, or by treating with acids such as liquid hydrofluoric acid, sulfonic acids, hydrochloric acid, hydrobromic acid, formic acid and the like.
In the following, synthesis examples of condensed heterocyclic derivatives, which are novel intermediates of the compounds of the present invention represented by formulae [III] and [V], are provided as reference examples.
37 g of ammonium acetate and 2.1 g of sodium cyanoborohydride were added to a solution containing 10 g of 2-(5-nitrobenzofuranyl) methyl ketone dissolved in 500 ml of methanol, and the resultant mixture was stirred for 30 hours at room temperature. The reaction mixture was then concentrated under reduced pressure, and acidified with concentrated hydrochloric acid. 300 ml of ethyl ether and 200 ml of water were then added thereto. Subsequently, the resultant water layer was made basic with a 5% aqueous solution of sodium hydroxide, the solution was extracted with 300 ml of ethyl ether, and then washed with water. The organic layer was then dried over anhydrous sodium sulfate, and the ether was removed under reduced pressure to yield 4.0 g of light brown granular crystals as the desired product (melting point: 53°-59° C.).
2.2 g of O-methylhydroxylamine hydrochloride and 1.3 g of potassium acetate were added to a solution containing 2.8 g of 2-acethyl-6-chlorobenzo[b]thiophene dissolved in 50 ml of methanol, and the resultant mixture was agitated under reflux for 1 hour. The undissolved material was then filtered off, and the methanol was removed. Subsequently, the residue was extracted with ethyl acetate, washed sequentially with 5% hydrochloric acid, a 5% aqueous solution of sodium bicarbonate, and water, and dried over anhydrous magnesium sulfate, and then concentrated.
Subsequently, 2.7 g of the crude 6-chloro-2-(1-methoxyiminoethyl)benzo[b]thiophene obtained was dissolved in 10 ml of dimethoxyethane, and the resultant solution was added dropwise at room temperature to a suspension of 0.85 g of sodium borohydride in 20 ml of dimethoxyethane. After agitating for 5 minutes at the same temperature, a solution containing 4.26 g of a boron trifluoride.diethyl ether complex in 5 ml of dimethoxyethane was then added dropwise at room temperature. After stirring for 30 minutes at the same temperature, the mixture was stirred for an additional 2 hours under reflux. The mixture was then allowed to cool to room temperature, after which 10% hydrochloric acid was added, adjusting the mixture to a pH of 3-4. The dimethoxyethane layer was concentrated and combined with the water layer, and the pH was raised to 7-8 using sodium carbonate. Extraction was then performed using dichloromethane, and the dichloromethane layer was then washed with water, dried over anhydrous magnesium sulfate, filtered through FLORISIL®, and concentrated to yield 0.35 g of the desired product, a transparent viscous fluid (refractive index nD 20 =1.5973).
Specific examples of intermediate compound represented by formula [III] obtained through the operations of Reference Examples 1 and 2 are shown in Table 8.
4.0 g of ammonium acetate and 0.24 g of sodium cyanoborohydride were added to a solution containing 1.0 g of 2-(5-cyano-2,3-dihydrobenzofuranyl) methyl ketone (prepared according to the method stated in Org. Prep. Proced. Int. 4,265 (1972) ) in 50 ml of methanol, and the resultant mixture was stirred for 30 hours at room temperature. The reaction mixture was then concentrated under reduced pressure, acidified with concentrated hydrochloric acid. 100 ml of ethyl ether and 50 ml of water were then added thereto. Subsequently, the resultant water layer was made basic with an aqueous solution of sodium hydroxide and extracted with 200 ml of ether. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The ether was then removed under reduced pressure to yield 0.6 g of the desired product, a light-yellow oily substance (refractive index nD 20 =1.5719).
Specific examples of intermediate compound represented by formula [III] obtained through the operation of Reference Example 3 are shown in Table 9.
1.4 g of anhydrous methylamine hydrochloride was added to a 10 ml solution of 20% methylamine in methanol while agitating, following which 0.8 g of sodium cyanoborohydride was added in small portions. To the resultant solution, 2.8 g of 2-(5-chlorobenzofuranyl)ethyl ketone was added and the mixture was stirred for 20 hours at room temperature. The reaction mixture was then acidified with 10% hydrochloric acid, and the methanol was removed under reduced pressure. The remaining aqueous solution was then washed with chloroform and made basic with an aqueous solution of sodium hydroxide. The solution was then extracted with 200 ml of chloroform, washed with water, and dried over anhydrous magnesium sulfate. The chloroform was subsequently removed under reduced pressure to yield 1.9 g of the desired product, a light-yellow oily substance (refractive index nD 20 =1.5681).
5.0 g of N2 -tert-butoxycarbonyl-N1 -[1-(5-nitro-2-benzofuranyl)ethyl]-L-valinamide was dissolved in 100 ml of tetrahydrofuran, and placed in a flow of hydrogen chloride gas for 1 hour at room temperature. The reaction mixture was then concentrated under reduced pressure, and the residual crude crystals obtained were washed with acetone to yield 3.6 g of the desired product (melting point: 211°-216° C.).
11.3 g of N2 -tert-butoxycarbonyl-N1 -[1-(2-benzo[b]thienyl)ethyl]-L-valinamide was dissolved in 150 ml of ethyl acetate, and 20 ml of 6N hydrochloric acid was added to the resultant solution at room temperature. After agitating overnight at room temperature, the pH of the solution was adjusted to 7-8 with a saturated aqueous solution of sodium bicarbonate under water cooling. The ethyl acetate layer was then washed with water, dried over anhydrous magnesium sulfate, and concentrated to yield a crude product. This crude product was then refined on FLORISIL® column chromatography to yield 6.7 g of the desired product, a white solid substance (melting point: 70°-71° C.).
Specific examples of intermediate [V] obtained through the operations of Reference Examples 5 and 6 are shown in Table 10.
TABLE 8
______________________________________
##STR23##
Melting Point
Intermediate (°C.) or
Compound Refractive
No. Xn R.sup.4
R.sup.6
A Index (n.sub.D.sup.20)
______________________________________
3 6-F CH.sub.3
H S
4 6-CH.sub.3 CH.sub.3
H S
5 7-Cl CH.sub.3
H O 1.5866
6 6-Cl CH.sub.3
H O 1.5780
7 4-Cl CH.sub.3
H O 1.5861
8 7-CH.sub.3 CH.sub.3
H O 1.5649
9 5-CH.sub.3 CH.sub.3
H O 1.5671
10 4-CH.sub.3 CH.sub.3
H O 1.5698
11 5-F CH.sub.3
H O 1.5750
12 5-CO.sub.2 CH.sub.3
CH.sub.3
H O 1.5840
13 5-OCF.sub.3
CH.sub.3
H O not determined
14 5-SCH.sub.3
CH.sub.3
H O 1.6109
15 5-CN CH.sub.3
H O 49-52
16 5,6-Cl.sub.2
CH.sub.3
H O 1.5982
17 5-Cl, 4-CH.sub.3
CH.sub.3
H O 1.5780
18 H CH.sub.3
CH.sub.3
O
19 5-Cl CH.sub.3
CH.sub.3
O 1.5693
20 5-F CH.sub.3
H S 37-38
______________________________________
TABLE 9
______________________________________
##STR24##
Intermediate
Compound Refractive
No. Xn Index (n.sub.D.sup.20)
______________________________________
22 5-Cl 1.5580
23 5-F 1.5316
24 5-CH.sub.3
1.5402
______________________________________
TABLE 10
______________________________________
##STR25##
Intermediate
Compound Melting Point
No. Xn R.sup.4 A B (°C.)
______________________________________
28 5-Cl CH.sub.3
O HCl 184-189
29 5-CN CH.sub.3
O HCl 202-205
30 5-F CH.sub.3
O HCl 90-93
31 3-CH.sub.3
CH.sub.3
S 58-62
32 H H S 76-77
______________________________________
The methods for producing the compounds according to the present invention as well as the use of the compounds will be described in detail in the following examples.
0.4 g of N-methylpiperidine was added to a solution containing 0.8 g of N-tert-butoxycarbonyl-L-valine dissolved in 40 ml of dichloromethane, at -20° C. or lower. After the mixture was stirred for 10 minutes at the same temperature, 0.5 g of isobutyl chloroformate was added to the mixture at -40° C., and stirred for 1 hour between -40° C. and -15° C. 0.7 g of 1-(5-cyano-2-benzofuranyl)ethylamine was added to this mixture at -20° C., and then the reaction mixture was allowed to sit and warm naturally to room temperature, with stirring. Water was subsequently added to the reaction mixture. After the dichloromethane layer was washed successively with a 5% aqueous solution of sodium bicarbonate and water, the organic layer was dried over anhydrous magnesium sulfate and then condensed. The residue, which was a crude crystal, was purified by column chromatography on silica gel, thus obtaining 0.7 g of the desired product in the form of a white powder.
0.54 g of N-methylmorpholine, and subsequently 0.7 g of isopropyl chloroformate were added to a solution containing 1.57 g of N-[1-(5-chloro-2-benzofuranyl)ethyl]-2-amino-3-methylbutanamide hydrochloride dissolved in 40 ml of dichloromethane at -15° C. The mixture was allowed to sit and warm naturally to room temperature and stirred for 15 hours at room temperature. Water was subsequently added to the reaction mixture. After the dichloromethane layer was washed with water, the organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residue, which was a crude crystal, was purified by column chromatography on silica gel, thus obtaining 0.85 g of the desired product in the form of a white powder.
0.8 g of the diastereomeric mixture obtained firm the above reaction was separated using liquid chromatography. The first eluted ingredient and the second eluted ingredient were condensed, thus obtaining 0.4 g of the desired diastereomer in the form of a white powder.
0.17 g of N-methylmorpholine, and subsequently 0.18 g of isopropyl chloroformate were added to a solution containing 0.5 g of N-[1-(5-nitro-2-benzofuranyl)ethyl]-2-amino-3-methylbutanamide dissolved in 40 ml of dichloromethane, at -15° C. The mixture was allowed to sit and warm naturally to room temperature and stirred for 15 hours at room temperature. Water was subsequently added to the reaction mixture. After the dichloromethane layer was washed with water, the organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residue, which was a crude crystal, was purified by column chromatography on silica gel, thus obtaining 0.1 g of the desired product in the form of a white powder.
4.7 g of N-methylpiperidine was added to a solution containing 9.7 g of N-isopropoxycarbonyl-L-valine dissolved in 100 ml of dichloromethane, at -20° C. and the mixture was stirred for 15 minutes at the same temperature. Subsequently, 6.5 g of isobutyl chloroformate was added to the mixture at -30° C. and then the whole mixture was stirred between -30° C. and -20° C. for 30 minutes. 8.5 g of 1-(5-fluoro-2-benzofuranyl)ethylamine was then added to the mixture at -50° C. The mixture was allowed to sit and warm naturally to room temperature and then stirred for 15 hours at room temperature. Water was subsequently added to the reaction mixture. After the dichloromethane layer was washed with water, the organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residue, which was a crude crystal, was purified by column chromatography on silica gel, thus obtaining 10.6 g of the desired product in the form of a white powder.
2.6 ml of a 1M aqueous solution of sodium bicarbonate and 0.62 g of di-tert-butyldicarbonate were added to a stirred solution containing 0.8 g of 2-amino-N-[1-(5-chloro-2-benzofuranyl)ethyl]-2,3-dimethylbutananamide dissolved in 15 ml of dioxane/water (2/1), at 0° C. The reaction mixture was stirred for 30 minutes at room temperature and then condensed. The residue was extracted with ethyl acetate and the organic layer was washed with water, subsequently dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The residue was purified by column chromatography on silica gel, thus obtaining 0.52 g of the desired product in the form of a white powder.
0.34 g of N-methylmorpholine and 0.57 g of N-methyl-N-phenylcarbamoyl chloride were successively added to a solution containing 1.1 g of N-[1-(5-chloro-2-benzofuranyl)ethyl]-2-amino-3-methylbutanamide hydrochloride dissolved in 30 ml of dichloromethane, at -15° C. The mixture was allowed to sit and warm naturally to room temperature and then stirred for 15 hours at room temperature. Water was subsequently added to the reaction mixture. After the dichloromethane layer was washed with water, the organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residual crude crystal was purified by column chromatography on silica gel, thus obtaining 1.1 g of the desired product in the form of a white powder.
0.5 g of N-methylpiperidine was added to a solution containing 1.3 g of N-tert-butoxycarbonyl-L-valine dissolved in 25 ml of dichloromethane, at -20° C. or lower. The reaction mixture was stirred at the same temperature for 10 minutes. Furthermore, 0.7 g of isobutyl chloroformate was added to the mixture at -40° C. and then stirred between -40° C. and -15° C. for 1 hour. 1.0 g of 1-[3-methyl-2-benzo[b]thienyl]ethylamine was added to the mixture at -20° C. The mixture was allowed to sit and warm naturally to room temperature with stirring. Water was subsequently added to the reaction mixture. After the dichloromethane layer was washed successively with a 5% aqueous solution of sodium bicarbonate and water, the organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residual crude crystal was purified by column chromatography on silica gel, thus obtaining 0.8 g of the desired product as a white powder.
5.1 g of N-methylpiperidine was added to a solution containing 10.4 g of N-isopropoxycarbonyl-L-valine dissolved in 200 ml of dichloromethane, at -20° C. and then 7.0 g of isobutyl chloroformate was added dropwise to the mixture. After the mixture was stirred at -20° C. for 10 minutes, 10.0 g of 1-(5-fluorobenzo[b]thiophen-2-yl)ethylamine was added to the mixture at -50° C. After stirring at the same temperature, the mixture was allowed to sit and warm naturally to room temperature and then stirred for 15 hours at room temperature. After the reaction mixture was washed successively with 10% hydrochloric acid, a saturated aqueous solution of sodium bicarbonate, and water, the organic layer was then dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by column chromatography on silica gel, thus obtaining 12.3 g of the desired product in the form of a white powder.
2.4 g of N-methylpiperidine was added to a solution containing 3.1 g of N-tert-butoxycarbonyl-L-valine dissolved in 80 ml of dichloromethane, at -20° C. or lower and then the mixture was stirred at the same temperature for 10 minutes. 2.0 g of isobutyl chloroformate was added to the mixture at -40° C. and the entire mixture was stirred between -40° C. and -15° C. for 1 hour. 2.5 g of 1-(3-methyl-2-indolyl)ethylamine was then added to the mixture at -20° C. The mixture was allowed to sit and warm naturally to room temperature and then stirred for 12 hours at room temperature. Water was subsequently added to the reaction mixture. After the dichloromethane layer was washed successively with a 5% aqueous solution of sodium bicarbonate and water, the organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residue was purified by column chromatography on silica gel, thus obtaining 2.5 g of the desired product in the form of a white powder.
0.37 g of N-methylpiperidine was added to a solution containing 0.8 g of N-tert-butoxycarbonyl-L-valine dissolved in 20 ml of dichloromethane, at -20° C. or lower and then the mixture was stirred at the same temperature for 10 minutes. 0.51 g of isobutyl chloroformate was added to the mixture at -40° C. and the entire mixture was stirred between -40° C. and -15° C. for 1 hour. 0.6 g of 1-(2,3-dihydro-2-benzofuranyl)ethylamine was added to the mixture at -20° C. The mixture was allowed to sit and warm naturally to room temperature with stirring. Water was then added to the reaction mixture. After the dichloromethane layer was washed successively with a 5% aqueous solution of sodium bicarbonate and water, the organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residual crude crystal was purified by column chromatography on silica gel, thus obtaining 0.5 g of the desired product in the form of a white powder.
0.7 g of N-methylpiperidine was added to a solution containing 1.5 g of N-tert-butoxycarbonyl-L-valine dissolved in 50 ml of dichloromethane, at -20° C. or lower and then the mixture was stirred at the same temperature for 10 minutes. 0.9 g of isobutyl chloroformate was added to the mixture at -40° C. and the entire mixture was stirred at -40° C.--15° C. for 1 hour. 1.1 g of 1-(3-indolyl)ethylamine was added to the mixture at -20° C. The mixture was allowed to sit and warm naturally to room temperature and then stirred at room temperature for 12 hours. Water was subsequently added to the reaction mixture. After the dichloromethane layer was washed successively with a 5% aqueous solution of sodium bicarbonate and water, the organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residual crude crystal was purified by column chromatography on silica gel, thus obtaining 0.4 g of the desired product in the form of a reddish-brown powder.
The agricultural or horticultural fungicide according to the present invention is a composition containing a condensed heterocyclic derivative represented by formula [I] as an active ingredient. In the case where the compounds according to the present invention are employed as an agricultural or horticultural fungicide, the compounds acting as the active ingredient can be formulated appropriately, depending on the purpose. The active ingredient is usually diluted in an inert liquid or a solid carder, and a surfactant, a dispersant, an adjuvant, and the like are added thereto if necessary. The mixture is then formulated in a known manner into, for example, a fine powder, a wettable powder, an emulsifiable concentrate, granules, or the like.
Suitable examples of carders employed in the formulation are solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermicuIite, slaked lime, siliceous sand, ammonium sulfate, urea, or the like; and liquid carders such as isopropyl alcohol, xylene, cyclohexanone, methylnaphthalene, and the like. Illustrative examples of the surfactants and dispersants include salts of dinaphthylmethanesulfonic acid, alkylarylsulfonic acid, and ligninesulfonic acid, sulfate esters of alcohol, polyoxyethylene glycol ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylenesorbitan monoalkylates, and the like. Suitable examples of auxiliary agents include carboxymethylcellulose, and the like. These preparations can be applied directly, or after diluting the preparation to a suitable concentration.
The agricultural or horticultural fungicide according to the present invention can be employed for a number of purposes: for example, treating seeds, spraying of stem and leaf portions, injection into the applying water, and applying into the soil. The proportion of the active ingredient is selected as needed. When formulated into a fine powder or granules, 0.1% by weight to 20% by weight of the active ingredient is preferred. For an emulsifiable concentrate or wettable powder, 5% by weight to 80% by weight of the active ingredient is adequate.
The rate of application of the agricultural or horticultural fungicide according to the present invention may vary depending on the type of active compound employed, the kind of the pest or disease to be controlled, the nature of occurrence of the pest or disease, the degree of damage, environmental conditions, the form of preparation to be used, and the like. When the agricultural or horticultural fungicide of the present invention is applied directly in the form of fine powder or granules, it is recommended that the rate of application of the active ingredient be suitably chosen within the range of 0.1 g to 5 kg per 10 ares, preferably, in the range of 1 g to 1 kg per 10 ares. In addition, when the fungicide of the present invention is in the form of a liquid such as an emulsifiable concentrate or a wettable powder, it is recommended that the ratio for application of the active ingredient be suitably chosen within the range of 0.1 ppm to 10,000 ppm, and preferably within the range of 10 ppm to 3,000 ppm.
The compounds according to the present invention in the formulation described above can control plant diseases caused by fungi belonging to Oomycetes, Ascomycetes, Deuteromycetes, and Basidiomycetes or other pathogenic fungi. The fungi include, but are not limited to, Pseudoperonospora such as cucumber downy mildew (Pseudoperonospora cubensis), Phytophthora such as tomato late blight (Phytophthora infestans), and Plasmopara such as grape downy mildew (Plasmopara viticola).
The agricultural or horticultural fungicide according to the present invention may be employed alone or in combination with other fungicides, insecticides, herbicides, plant growth modifiers, fertilizers or the like.
Next, the representative formulations are illustrated with reference to the following Formulation Examples, wherein all "%" represent "percent by weight".
Two % of Compound (59), 5% of diatomaceous earth, and 93% of clay were uniformly mixed and ground into a fine powder.
Fifty % of Compound (70), 45% of diatomaceous earth, 2% of sodium dinaphthylmethanedisulfonate, and 3% of sodium ligninsulfonate were uniformly mixed and ground into a wettable powder.
Thirty % of Compound (5), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate, and 35% of methylnaphthalene were uniformly dissolved, thus obtaining an emulsifiable concentrate.
Five % of Compound (16), 2% of sodium lauryl sulfonate, 5% of sodium lignin sulfonate, 2% of carbomethylcellulose, and 86% of clay were mixed and ground. One hundred parts by weight of the ground n-fixture was added to 20 parts by weight of water. The resulting mixture was kneaded and formed into granules of 14 mesh to 32 mesh by means of an extrusion granulator, and then dried into the desired granules.
The agricultural or horticultural fungicides according to the present invention exhibit high ability to control the growth or spread of cucumber downy mildew (Pseudoperonospora cubensis), tomato late blight (Phytophthora infestans), and grape downy mildew (Plasmopara viticola), and are effective for potato late blight (Phytophthora infestans). In addition, the agricultural or horticultural fungicides according to the present invention not only exhibit the ability to present fungal infection, but also exhibit the ability to eliminate pathogenic fungi after it has invaded a host plant. Furthermore, the agricultural or horticultural fungicides of the present invention are also characterized in that they are not harmful chemicals and exhibit excellent characteristics such as systemic action, residual activity, and the influence of rain-fall on effect.
The effects of the compounds according to the present invention are now illustrated with reference to the following Test Examples.
Cucumber seeds (variety: "Sagami hanjiro") were sown at a rate of 10 seeds each in a square PVC(polyvinyl chloride) pot, wherein each side is 9 cm wide. The seeds were allowed to grow in a greenhouse, for 7 days, to the cotyledonous stage. A wettable powder prepared as in Formulation Example 2 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then applied at a rate of 10 ml per pot to the cucumber seedlings at their cotyledonous stage. After drying in the air, the plant was inoculated with a spore suspension of cucumber downy mildew (Pseudoperonospora cubensis) fungi and then placed in a moist chamber at 22° C. for 24 hours, and then placed in a green house. On the seventh day after the inoculation, the extent of lesion was rated in accordance with the following standards of evaluation in order to secure the preventive effects of the compounds according to the present invention. The results of the test are given in Table 11.
Standards of Evaluation:
Class A: No lesions were observed.
Class B: Incidence area is less than 25%.
Class C: Incidence area is 25% or more and less than 50%.
Class D: Incidence area is 50% or more.
For comparison, N2 -(t-butoxycarbonyl)-N1 -(3-pyridylmethyl)-L-valinamide (Comparative Compound A, hereinafter referred to as "CA") and N2 -(phenoxycarbonyl)-N1 -[1-(2-furyl)ethyl]-L-valinamide (Comparative Compound B, hereinafter referred to as "CB") which are disclosed as active ingredients for fungicides in Japanese Patent Application First Publication No. Hei 3-5451 and Japanese Patent Application First Publication No. Hei 3-153657, respectively, were employed. These comparative compounds were formulated in a similar manner as the compounds of the present invention to be tested.
TABLE 11 ______________________________________ Compound No. Evaluation ______________________________________ 1 A 2 A 4 B 5 A 6 A 7 B 8 B 9 B 10 A 11 A 12 A 13 A 14 B 15 A 16 A 17 A 18 A 19 A 20 A 23 A 25 A 27 B 28 B 29 B 33 A 40 B 55 A 56 A 58 A 59 A 60 A 61 A 63 A 64 B 66 B 67 A 68 A 69 A 70 A 71 A 72 A 73 B 76 A 77 A 79 A 80 A 83 A 90 B 92 A 93 A 94 B 97 A 99 A 100 A 101 A 102 A 104 A 105 A 106 A 107 A 108 A 109 A 110 A 111 A 112 A 114 A 115 A 116 A 117 A 118 A 119 A 120 A 121 A 128 B 151 B 156 A 157 A 158 A 159 A 161 A 163 A 165 A 166 A 167 A 168 A 169 A 170 A 171 B 177 A 178 A 179 A 180 A 181 A 182 B 192 A 193 A 194 A 200 A 204 A 205 A 206 B 228 A 230 B 233 A 234 A 235 B 304 B 307 B 313 A 314 A 315 B 316 A 217 A 318 A 319 A 320 A 321 A 322 B 323 B 324 A 325 A 326 A 327 A 328 B 330 A 331 A 332 B 335 A 336 A 337 A 344 A 350 B 351 A 352 A 353 A 356 A 357 A 358 A 359 A 360 A 362 A 363 A 364 A 365 A 366 A 367 A 368 A 370 A 376 A 377 A 378 A 380 A 381 A 382 A 383 A 384 A 385 A 386 A 387 A 388 A 389 A 393 A 395 A 397 A 398 A 399 A 401 A 402 A 403 A 404 A 407 A 413 A 414 A 423 B CA D CB D ______________________________________
Cucumber seeds (variety: "Sagami hanjiro") were sown at a rate of 10 seeds each in a square PVC (polyvinyl chloride) pot, wherein each side is 9 cm wide. The seeds were allowed to grow in a greenhouse, for 7 days, to the cotyledonous stage. The seedlings were inoculated with a spore suspension of cucumber downy mildew (Pseudoperonospora cubensis) fungi and then placed in a moist chamber at 22° C. for 24 hours. After drying in the air, a wettable powder prepared as in Formulation Example 2 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then applied at a rate of 10 ml per pot to the cucumber seedlings. The seedlings were then placed in a green house. On the seventh day after the inoculation, the extent of lesion was rated in accordance with the following standards of evaluation in order to secure the effect of treating with the compounds according to the present invention. The same Comparative Compounds as disclosed in Test Example 1 were employed. The results of the test are given in Table 12.
Evaluation standards:
Class A: No lesions were observed.
Class B: Incidence area is less than 25%.
Class C: Incidence area is 25% or more and less than 50%.
Class D: Incidence area is 50% or more.
TABLE 12 ______________________________________ Compound No. Evaluation ______________________________________ 6 B 12 B 13 B 16 A 17 A 19 B 23 A 25 B 33 A 58 A 59 A 60 A 63 B 68 A 69 B 70 A 71 A 72 A 76 A 77 B 80 A 83 B 97 A 99 B 100 B 101 A 102 A 104 A 105 A 107 A 108 A 109 A 112 A 114 B 115 A 116 A 117 A 119 A 120 A 157 A 158 B 161 B 163 A 165 A 169 A 177 B 179 B 180 A 192 A 193 B 194 A 200 A 204 A 233 B 313 A 316 A 317 A 319 A 320 A 321 A 325 B 326 A 327 A 331 B 335 A 336 B 337 A 344 A 351 A 352 A 353 A 356 B 357 A 358 A 359 A 360 A 362 A 363 A 370 A 376 A 380 A 381 B 382 A 383 B 387 A 388 A 389 A 393 A 395 A 397 A 398 A 399 A 401 A 402 A 403 A 414 B CA D CB D ______________________________________
One tomato seedling (variety: "Ponterosa") was transplanted in each porcelain pot (diameter: 9 cm) and grown in a greenhouse. A wettable powder prepared as in Formulation Example 2 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then applied at a rate of 20 ml per pot to the tomato seedlings at their 6- or 7-leaf stage. After drying in the air, the plant was inoculated with a zoosporangium suspension of tomato late blight (Phytophthora infestans) fungi and then placed in a moist chamber at 22° C. On the fourth day after the inoculation, index of incidence was determined based on the incidence area. The degree of damage and the ability to prevent the disease (controlling activity) were calculated according to the following standards. The results of the test are shown in Table 13. The same Comparative Compounds (CA and CB) as disclosed in Test Example 1 were employed.
Standard of Test
Incidence Index 0: No lesions
Incidence Index 1: Incidence area is less than 5%
Incidence Index 2: Incidence area is 5% or more and less than 33.3%
Incidence Index 3: Incidence area is 33.3% or more and less than 66.6%
Incidence Index 4: Incidence area is 66.6% or more ##EQU1##
TABLE 13 ______________________________________ Compound No. Controlling Activity (%) ______________________________________ 2 100 6 100 16 100 17 100 20 100 23 100 25 100 33 100 55 100 56 100 58 100 59 100 60 100 63 100 67 100 68 100 69 100 70 100 71 100 72 100 76 100 77 100 79 100 80 100 83 100 92 100 93 100 97 100 99 100 100 100 101 100 102 100 104 100 105 100 106 100 107 100 108 100 109 100 110 100 111 100 112 100 114 100 115 100 116 100 117 100 118 100 119 100 120 100 121 100 156 100 157 100 158 100 159 100 161 100 163 100 165 100 166 100 169 100 177 100 178 100 179 100 180 100 192 100 193 100 194 100 200 100 204 100 233 100 234 100 313 100 314 100 316 100 317 100 319 100 320 100 321 100 325 100 327 100 331 100 335 100 336 100 337 100 344 100 351 100 352 100 353 100 356 100 357 100 358 100 359 100 360 100 362 100 363 100 364 100 366 100 367 100 368 100 370 100 376 100 377 100 378 100 380 100 381 100 382 100 383 100 384 100 385 100 386 100 387 100 388 100 389 100 393 100 395 100 397 100 398 100 399 100 401 100 402 100 403 100 CA 2 CB 5 ______________________________________
One grape seedling (variety: "Kyoho") each was grown by cutting and pruned in a porcelain pot (diameter: 12 cm) and maintained in a greenhouse. A wettable powder prepared as in Formulation Example 2 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then applied at a rate of 20 ml per pot to the grape seedlings at their 4- or 5-leaf stage. After drying in the air, the plant was inoculated with a zoosporangium suspension of grape downy mildew (Plasmopara viticola) fungi and then placed in a moist chamber at 22° C. for 24 hours. On the seventh day in the greenhouse after the inoculation, the plant was again placed in a moist chamber at 22° C. for 24 hours to cultivate conidiospores. The incidence area where conidiospores were grown in each leaf was examined and determined the incidence index according to the following standards. The degree of damage and ability to prevent the disease (controlling activity) were calculated in the same manner as described in Test Example 3. The results of the test are shown in Table 14. The same Comparative Compounds as disclosed in Test Example 1 were employed.
Standard of Test
Incidence Index 0: No lesions
Incidence Index 1: Incidence area is less than 5%
Incidence Index 2: Incidence area is 5% or more and less than 33.3%
Incidence Index 3: Incidence area is 33.3% or more and less than 66.6%
Incidence Index 4: Incidence area is 66.6% or more
TABLE 14 ______________________________________ Compound No. Controlling Activity (%) ______________________________________ 2 100 6 100 16 100 17 100 20 100 23 100 25 100 33 100 55 100 56 100 58 100 59 100 60 100 63 100 67 100 68 100 69 100 70 100 71 100 72 100 76 100 77 100 79 100 80 100 83 100 92 100 93 100 97 100 99 100 100 100 101 100 102 100 104 100 105 100 106 100 107 100 108 100 109 100 110 100 111 100 112 100 114 100 115 100 116 100 117 100 118 100 119 100 120 100 121 100 156 100 157 100 158 100 159 100 161 100 163 100 165 100 166 100 169 100 177 100 178 100 179 100 180 100 192 100 193 100 194 100 200 100 204 100 233 100 234 100 313 100 314 100 316 100 317 100 319 100 320 100 321 100 325 100 327 100 331 100 335 100 336 100 337 100 344 100 351 100 352 100 353 100 356 100 357 100 358 100 359 100 360 100 362 100 363 100 364 100 366 100 367 100 368 100 370 100 376 100 377 100 378 100 380 100 381 100 382 100 383 100 384 100 385 100 386 100 387 100 388 100 389 100 393 100 395 100 397 100 398 100 399 100 401 100 402 100 403 100 CA 7 CB 52 ______________________________________
Claims (6)
1. A condensed heterocyclic derivative represented by a formula: ##STR26## wherein R1 represents a C1-C6 alkyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a cyano group, and a methoxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C8 cycloalkyl group optionally having at least one methyl group, a C3-C8 cycloalkenyl group optionally having at least one methyl group, a C2-C6 cyclic ether group optionally having at least one methyl group, a C7-C10 aralkyl group optionally having at least one substituent selected from the group consisting of a methyl group, a methoxy group, and a nitro group, a phenyl group optionally having at least one substituent selected from the group consisting of a halogen atom, a methyl group, a methoxy group, a nitro group, and a methoxycarbonyl group, a dimethylamino group, or an ethoxy carbonyl group,
R2, R3, R4, R5, and R6 independently represent a hydrogen atom, a C1-C6 alkyl group optionally having at least one halogen group, a C3-C6 cycloalkyl group, a C7-C10 aralkyl group; a phenyl group, a cyano group, an acyl group, a C1-C6 alkoxy group, or a C1-C6 alkoxycarbonyl group,
R2 may form a C3-C6 alkylic ring with R3 ;
Z is represented by the following formulae: ##STR27## wherein X represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having at least one halogen atom, a C2-C6 alkynyl group, a methoxy group, a trifluoromethoxy group, a hydroxyl group, a methoxycarbonyl group, a methylcarbonyloxy group, an amino group, a dimethylamino group, a nitro group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group, a phenyl group, an acetyl group, a formyl group, or a cyano group;
n is an integer of 1, 2, or 3;
A is O, S, N, or represented by the formula: ##STR28## wherein R7 represents a hydrogen atom, a methyl group, an acetyl group, or a benzoyl group; and
W is represented by --C(O)--, --SO2 --, --NHC(O)--, --N(CH3)C(O)--, --OC(O)--, --SC(O)--, --OC(S)--, or --SC(S)--.
2. A condensed heterocyclic derivative as recited in claim 1, wherein
R1 represents a C2-C6 straight or branched alkyl group, a C3 straight or branched alkenyl group, a C5-C6 cycloalkyl group, or a phenyl group,
R2 represents a hydrogen atom,
R3 represents an ethyl group, an isopropyl group, or a sec-butyl group,
R4 represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group,
R5 represents a hydrogen atom, or a methyl group,
R6 represents a hydrogen atom,
Z represents a substituted heterocyclic group including a benzofuran group, a benzothiophene group, an indole group, or a 2,3-dihydrobenzofuran which has one or two substituent selected from the group consisting of a fluorine atom, a chlorine atom, a nitro group, a cyano group, and a methyl group,
W is represented by --OC(O)--, and
wherein the carbon to which R2 and R3 are attached is in the S configuration.
3. A condensed heterocyclic derivative as recited in claim 1, wherein
R1 represents an isopropyl group, a tert-butyl group, a sec-butyl group, a cyclopentyl group, an isopropenyl group, or a phenyl group,
R2 represents a hydrogen atom,
R3 represents an ethyl group, an isopropyl group, or a sec-butyl group,
R4 represents a methyl group,
R5 represents a hydrogen atom,
R6 represents a hydrogen atom,
Z represents a substituted heterocyclic group including a benzofuran group or a benzothiophene which has one or two substituent selected from the group consisting of a fluorine atom, a chlorine atom, a nitro group, a cyano group, and a methyl group,
W is represented by --OC(O)--, and
wherein the carbon to which R2 and R3 are attached is in the S configuration.
4. A condensed heterocyclic derivative as recited in claim 1, wherein the derivative includes N1 -[1-(5-chloro-2-benzofuranyl)ethyl]-N2 -cyclopentyloxycarbonyl-L-valinamide, N1 -[1-(5-chloro-2-benzofuranyl)ethyl]-N2 -isopropyloxycarbonyl-L-valinamide, N1 -[1-(5-fluoro-2-benzofuranyl)ethyl]-N2 -isopropyloxycarbonyl-L-valinamide, N2 -isopropyloxycarbonyl-N1 -[1-(5-nitro-2-benzofuranyl)ethyl]-L-valinamide, N1 -[1-(5-fluoro-2-benzo[b]thienyl)ethyl]-N2 -isopropyloxycarbonyl-L-valinamide, N1 -[1-(6-fluoro-2-benzo[b]thienyl)ethyl]-N2 -isopropyloxycarbonyl-L-valanimide, N2 -sec-butyloxycarbonyl-N1 -[1-(5-chloro-2-benzofuranyl)ethyl]-L-valinamide, or N1 -[1-(5-chloro-2-benzofuranyl)ethyl]-N2 -phenoxycarbonyl-L-valinamide.
5. An agricultural or horticultural fungicide which comprises an effective amount of a condensed heterocyclic derivative, as recited in claim 1, known to be effective as a fungicide and a diluent.
6. A method for controlling fungi which infect agricultural or horticultural nonfungal, photosynthetic plants comprising the step of applying an effective amount of a condensed heterocyclic derivative, as recited in claim 1, known to be effective as a fungicide to the plants.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26271892 | 1992-09-07 | ||
| JP4-262718 | 1993-01-28 | ||
| JP5-31117 | 1993-01-28 | ||
| JP3111793 | 1993-01-28 | ||
| JP20825893A JP3283114B2 (en) | 1992-09-07 | 1993-07-30 | Condensed heterocyclic derivatives and agricultural and horticultural fungicides |
| JP5-208258 | 1993-07-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5348976A true US5348976A (en) | 1994-09-20 |
Family
ID=27287207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/117,284 Expired - Lifetime US5348976A (en) | 1992-09-07 | 1993-09-07 | Condensed heterocyclic derivatives and agricultural or horticultural fungicides containing the same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5348976A (en) |
| EP (1) | EP0587110B1 (en) |
| JP (1) | JP3283114B2 (en) |
| KR (1) | KR0139185B1 (en) |
| CN (3) | CN1036195C (en) |
| DE (1) | DE69315774T2 (en) |
| RU (1) | RU2098408C1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5554641A (en) * | 1995-03-20 | 1996-09-10 | Horwell; David C. | Nonpeptides as tachykinin antagonists |
| US5674890A (en) * | 1993-02-15 | 1997-10-07 | Sanofi | Compounds bearing sulphamoyl and amidino radicals, their preparation process and pharmaceutical compositions containing them |
| US6034256A (en) * | 1997-04-21 | 2000-03-07 | G.D. Searle & Co. | Substituted benzopyran derivatives for the treatment of inflammation |
| US6077850A (en) * | 1997-04-21 | 2000-06-20 | G.D. Searle & Co. | Substituted benzopyran analogs for the treatment of inflammation |
| US20050143452A1 (en) * | 2003-10-24 | 2005-06-30 | Wyeth | Dihydrobenzofuranyl alkanamine derivatives and methods for using same |
| US20050261347A1 (en) * | 2003-10-24 | 2005-11-24 | Wyeth | Dihydrobenzofuranyl alkanamine derivatives and methods for using same |
| US20060258714A1 (en) * | 2005-04-22 | 2006-11-16 | Wyeth | Chromane and chromene derivatives and uses thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO112859B1 (en) * | 1993-04-28 | 1998-01-30 | Kumiai Chemical Industry Co., Ltd. | Aminoacid amide derivatives, process for preparation and fungicides comprising said derivatives |
| DE19501175A1 (en) * | 1994-06-28 | 1996-01-04 | Bayer Ag | Amino acid derivatives |
| CN1234681C (en) * | 1994-06-28 | 2006-01-04 | 拜尔公司 | Amino acid derivatives and their use as pesticides |
| GB9723407D0 (en) | 1997-11-05 | 1998-01-07 | Ciba Geigy Ag | Organic compounds |
| JP2002538151A (en) | 1999-03-02 | 2002-11-12 | ベーリンガー インゲルハイム ファーマシューティカルズ インコーポレイテッド | Compounds useful as reversible inhibitors of cathepsin |
| SI1178958T1 (en) * | 1999-03-15 | 2004-08-31 | Axys Pharmaceuticals, Inc. | N-cyanomethyl amides as protease inhibitors |
| US6420364B1 (en) | 1999-09-13 | 2002-07-16 | Boehringer Ingelheim Pharmaceuticals, Inc. | Compound useful as reversible inhibitors of cysteine proteases |
| GB0003111D0 (en) | 2000-02-10 | 2000-03-29 | Novartis Ag | Organic compounds |
| CN102452959A (en) * | 2010-10-20 | 2012-05-16 | 中国农业科学院植物保护研究所 | Substituted valinamide derivatives and preparation thereof |
| CN105037208B (en) * | 2015-06-18 | 2017-06-06 | 南开大学 | A kind of N (the substitution ethyl of 1 methyl 2) valine amide carbamate derivatives and application |
| CN105037207B (en) * | 2015-06-18 | 2017-05-17 | 南开大学 | (Iso-)leucinamide carbamate derivative and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4628058A (en) * | 1984-03-24 | 1986-12-09 | Basf Aktiengesellschaft | N-(2,3-dihydrobenzofuran-2-yl)-azolylureas and fungicides containing these compounds |
| US4742077A (en) * | 1985-09-14 | 1988-05-03 | Sandoz Ltd. | Bicyclic allylether derivatives, processes for their production and their use |
| EP0398072A2 (en) * | 1989-05-13 | 1990-11-22 | Bayer Ag | Amino-acid amides |
| EP0425925A2 (en) * | 1989-11-01 | 1991-05-08 | Bayer Ag | Substituted amino acid amide derivatives, their preparation and use |
| EP0477639A1 (en) * | 1990-09-22 | 1992-04-01 | Bayer Ag | Substituted amino acid amide derivatives, their preparation and use |
| US5106866A (en) * | 1984-06-09 | 1992-04-21 | Kaken Pharmaceutical Co., Ltd. | Amine derivatives, processes for preparing the same and fungicides containing the same |
| EP0493683A1 (en) * | 1990-12-20 | 1992-07-08 | American Cyanamid Company | Fungicidal amino acid amides |
| US5134140A (en) * | 1991-06-21 | 1992-07-28 | American Home Products Corporation | Psychotropic benzofuran derivatives |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4029472C1 (en) * | 1990-09-17 | 1991-10-24 | Schuetz-Werke Gmbh & Co Kg, 5418 Selters, De |
-
1993
- 1993-07-30 JP JP20825893A patent/JP3283114B2/en not_active Expired - Fee Related
- 1993-09-06 RU RU9393051174A patent/RU2098408C1/en not_active IP Right Cessation
- 1993-09-07 DE DE69315774T patent/DE69315774T2/en not_active Expired - Fee Related
- 1993-09-07 KR KR1019930017947A patent/KR0139185B1/en not_active IP Right Cessation
- 1993-09-07 CN CN93119072A patent/CN1036195C/en not_active Expired - Fee Related
- 1993-09-07 US US08/117,284 patent/US5348976A/en not_active Expired - Lifetime
- 1993-09-07 EP EP93114325A patent/EP0587110B1/en not_active Expired - Lifetime
-
1996
- 1996-07-30 CN CN96111474A patent/CN1062270C/en not_active Expired - Fee Related
- 1996-07-30 CN CN96111473A patent/CN1062264C/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4628058A (en) * | 1984-03-24 | 1986-12-09 | Basf Aktiengesellschaft | N-(2,3-dihydrobenzofuran-2-yl)-azolylureas and fungicides containing these compounds |
| US5106866A (en) * | 1984-06-09 | 1992-04-21 | Kaken Pharmaceutical Co., Ltd. | Amine derivatives, processes for preparing the same and fungicides containing the same |
| US4742077A (en) * | 1985-09-14 | 1988-05-03 | Sandoz Ltd. | Bicyclic allylether derivatives, processes for their production and their use |
| EP0398072A2 (en) * | 1989-05-13 | 1990-11-22 | Bayer Ag | Amino-acid amides |
| EP0425925A2 (en) * | 1989-11-01 | 1991-05-08 | Bayer Ag | Substituted amino acid amide derivatives, their preparation and use |
| EP0477639A1 (en) * | 1990-09-22 | 1992-04-01 | Bayer Ag | Substituted amino acid amide derivatives, their preparation and use |
| EP0493683A1 (en) * | 1990-12-20 | 1992-07-08 | American Cyanamid Company | Fungicidal amino acid amides |
| US5134140A (en) * | 1991-06-21 | 1992-07-28 | American Home Products Corporation | Psychotropic benzofuran derivatives |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674890A (en) * | 1993-02-15 | 1997-10-07 | Sanofi | Compounds bearing sulphamoyl and amidino radicals, their preparation process and pharmaceutical compositions containing them |
| US5554641A (en) * | 1995-03-20 | 1996-09-10 | Horwell; David C. | Nonpeptides as tachykinin antagonists |
| US6806288B1 (en) | 1997-04-21 | 2004-10-19 | G.D. Searle & Co. | Substituted benzopyran derivatives for the treatment |
| US6077850A (en) * | 1997-04-21 | 2000-06-20 | G.D. Searle & Co. | Substituted benzopyran analogs for the treatment of inflammation |
| US6271253B1 (en) | 1997-04-21 | 2001-08-07 | G.D. Searle & Co. | Substituted benzopyran derivatives for the treatment of inflammation |
| US6492390B2 (en) | 1997-04-21 | 2002-12-10 | G.D. Searle & Co. | Substituted benzopyran analogs for the treatment of inflammation |
| US6034256A (en) * | 1997-04-21 | 2000-03-07 | G.D. Searle & Co. | Substituted benzopyran derivatives for the treatment of inflammation |
| US20050049252A1 (en) * | 1997-04-21 | 2005-03-03 | G.D. Searle & Co. | Substituted benzopyran derivatives for the treatment of inflammation |
| US7109211B2 (en) | 1997-04-21 | 2006-09-19 | Pharmacia Corporation (Of Pfizer, Inc.) | Substituted benzopyran derivatives for the treatment of inflammation |
| US20050143452A1 (en) * | 2003-10-24 | 2005-06-30 | Wyeth | Dihydrobenzofuranyl alkanamine derivatives and methods for using same |
| US20050261347A1 (en) * | 2003-10-24 | 2005-11-24 | Wyeth | Dihydrobenzofuranyl alkanamine derivatives and methods for using same |
| US7435837B2 (en) | 2003-10-24 | 2008-10-14 | Wyeth | Dihydrobenzofuranyl alkanamine derivatives and methods for using same |
| US20060258714A1 (en) * | 2005-04-22 | 2006-11-16 | Wyeth | Chromane and chromene derivatives and uses thereof |
| US7365095B2 (en) | 2005-04-22 | 2008-04-29 | Wyeth | Chromane and chromene derivatives and uses thereof |
| US20080182891A1 (en) * | 2005-04-22 | 2008-07-31 | Wyeth | Chromane and chromene derivatives and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR0139185B1 (en) | 1998-05-15 |
| CN1062270C (en) | 2001-02-21 |
| JP3283114B2 (en) | 2002-05-20 |
| CN1086810A (en) | 1994-05-18 |
| EP0587110A2 (en) | 1994-03-16 |
| CN1149054A (en) | 1997-05-07 |
| CN1154964A (en) | 1997-07-23 |
| CN1036195C (en) | 1997-10-22 |
| EP0587110B1 (en) | 1997-12-17 |
| RU2098408C1 (en) | 1997-12-10 |
| JPH06279405A (en) | 1994-10-04 |
| KR940007016A (en) | 1994-04-26 |
| DE69315774T2 (en) | 1998-05-07 |
| CN1062264C (en) | 2001-02-21 |
| DE69315774D1 (en) | 1998-01-29 |
| EP0587110A3 (en) | 1994-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5348976A (en) | Condensed heterocyclic derivatives and agricultural or horticultural fungicides containing the same | |
| US5789428A (en) | Amino-acid amide derivatives, processes for preparing the same, agricultural or horticultural fungicides, and method for killing fungi | |
| EP0648740B1 (en) | Amino acid amide derivative, agrohorticultural bactericide, and production process | |
| JPH04230652A (en) | Substituted valinamide derivative | |
| EP0171768B1 (en) | Substituted propargyloxyacetonitrile derivatives, process for production thereof, and herbicide and agricultural-horticultural fungicide comprising said derivatives as active ingredients | |
| RU2194040C2 (en) | Derivatives of pyrimidinylhydroxyalkaneamides and fungicides for agriculture or gardening | |
| JPH09323984A (en) | Amino acid amide derivatives and fungicides for agricultural and horticultural use | |
| KR900001196B1 (en) | Process for preparing pyrazol derivatives | |
| EP0313091B1 (en) | Amide derivatives, processes for production thereof, and agricultural-horticultural fungicide containing them | |
| EP0268892A2 (en) | Substituted-amido derivatives, method for preparation of the same and phytopathogenic fungicides containing the same | |
| KR0185970B1 (en) | Substituted amino acid amide derivatives, preparation method thereof and use thereof | |
| JPH0327360A (en) | Phenoxyalkylamine derivative and insecticide, miticide or sterilizing agent | |
| US5310747A (en) | Benzimidazole derivatives, agricultural and horticultural fungicides containing the same as an active ingredient and intermediate compounds thereof | |
| US5039696A (en) | Maleimide derivatives and fungicides for agriculture and horticulture containing the same | |
| KR102349000B1 (en) | Compound of N-naphthyl amide derivatives, preparation methods of the same, compositions for controlling fungal diseases comprising the same, and method of controlling plant diseases using the same | |
| JP3127386B2 (en) | Amino acid amide derivatives and fungicides for agricultural and horticultural use | |
| KR900003390B1 (en) | Pyrazol derivatives and agricultural and horticultural fungicides containing said compounds | |
| US5395952A (en) | Benzimidazole derivatives agricultural and horticultural fungicides containing the same as an active ingredient and intermediate compounds thereof | |
| US5472974A (en) | Benzimidazole derivatives, agricultural and horticultural fungicides containing the same as an active ingredient and intermediate compounds thereof | |
| KR100198752B1 (en) | Amino acid amide derivative preparation method and agricultural and horticultural fungicide | |
| JPH10182616A (en) | Amino acid amide derivatives and fungicides for agricultural and horticultural use | |
| JPH06157499A (en) | N-@(3754/24)1-substituted ethyl)-2,2-dichlorocyclopropane carboxamide derivative and germicide for agriculture and horticulture | |
| JPH09301954A (en) | N- (Fused Heteroarylalkyl) alkanoic acid amide derivative and agricultural / horticultural fungicide | |
| JPH01250379A (en) | Amide derivatives, their production methods, and agricultural and horticultural fungicides containing them as active ingredients | |
| JPS60255765A (en) | Pyrrole derivative, its production and herbicide and fungicide containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: IHARA CHEMICAL INDUSTRY CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SHIBATA, MASARU;ITO, SHIGEKAZU;SAKAI, JUN-ETSU;AND OTHERS;REEL/FRAME:007033/0344 Effective date: 19930830 Owner name: KUMIAI CHEMICAL INDUSTRY CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SHIBATA, MASARU;ITO, SHIGEKAZU;SAKAI, JUN-ETSU;AND OTHERS;REEL/FRAME:007033/0344 Effective date: 19930830 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 12 |
